沈阳地区臭氧污染日时空变化特征及天气分型研究

利用2013—2019年沈阳地区11个国控监测站近地层臭氧(O_3)浓度监测数据和地面气象观测资料,分析了沈阳地区O_3污染日的O_3浓度时空分布规律,并对造成O_3污染日的天气系统进行了主观分型。结果表明:自2013年以来,以O_3为首要污染物的天数逐年增加,2017年达到研究期内的最高值,但2018—2019年略有下降。O_3浓度的日变化趋势呈现明显的单峰形,O_3-1 h在10:00—20:00明显高于其他时间段,最大浓度值出现在15:00,而在01:00—07:00则相对较低。从季节变化上看,沈阳地区O_3污染主要发生在6—7月,两个月的O_3污染日之和占全年O_3总污染日的比例高达51%。从O_3浓度空间分布上看,沈阳地区三环外监测站测得的O_3浓度明显高于三环内监测站,高浓度区域主要集中在东部和东北部,城市中心存在明显的低浓度区,南部和北部差别不大,但也明显高于城市中心。造成沈阳地区O_3污染的主要天气类型有4种:暖脊型、均压场型、高空槽型和副热带高压型。其中:暖脊型出现的频次最高,占总样本的49.1%;副热带高压型出现的次数最少,占总样本的7.7%。     

北京市城区挥发性有机物污染特征及其对臭氧影响分析

对2020年4月—2021年3月北京市建成区挥发性有机物（VOCs）的化学特征、污染来源及其对臭氧（O₃）污染的影响进行了研究。结果显示：O₃日最大8 h滑动平均值在臭氧季（4—9月）均值为134 μg/m³，是非臭氧季（10月至次年3月）均值（59.6 μg/m³）的2.2倍。臭氧季VOCs体积浓度均值为14.3×10^-9，明显低于非臭氧季（21.1×10^-9），可能与光化学反应速率和VOCs来源的季节性差异有关。臭氧生成潜势（OFP）贡献率排名前10位的物种在臭氧季和非臭氧季相似，均包括间/对-二甲苯、甲苯、乙烯、邻二甲苯、异戊烷、正丁烷、丙烯、反式-2-丁烯和1，2，4-三甲基苯，但排名有所差异，燃煤源特征明显的乙烯等物种在非臭氧季上升明显，与溶剂使用、油气挥发相关的间/对二甲苯、甲苯、异戊烷和正丁烷等物种在臭氧季上升明显。甲苯/苯的值和异戊烷/正戊烷的值在臭氧季明显高于非臭氧季，反映出机动车排放和油气挥发等在臭氧季影响突出，非臭氧季是燃煤影响显著。基于正交矩阵因子分解模型（PMF），臭氧季解析出机动车尾气排放（40.9%）、溶剂使用（20%）、油气挥发（16.4%）、工业排放（17.6%）和植物排放（5.1%）等5种污染源；非臭氧季解析出机动车尾气（38.9%）、燃烧源（26.3%）、工业排放（17.8%）和溶剂使用（17%）等4种污染源。     

衡阳市区和衡山背景站臭氧浓度变化规律的对比分析

选取衡阳市区和衡山背景站臭氧自动监测数据,分析两地的臭氧污染特征。对空气质量的优良率情况、臭氧作为首要污染物的变化情况、臭氧浓度的日变化特征、典型时段的浓度变化特征、臭氧浓度的月际变化特征和臭氧与PM_(2.5)的关联情况等进行了分析。结果表明,多云及阴雨天气时,衡阳市区的臭氧浓度日变化幅度大于衡山背景站。夏季,衡阳市区和衡山背景站的臭氧浓度的日变化特征规律差异较大,臭氧浓度分布比较分散,前者为典型的单峰形,后者则波动平缓。冬季,日变化幅度不大,但衡阳市区的臭氧浓度明显低于衡山背景站。衡山背景站和衡阳市区的臭氧基本同步变化,但日均值高于衡阳市区。     

Analysis of crater formation in buried NG pipelines: A survey based on past accidents and evaluation of domino effect

The formation of a crater by the abrupt and catastrophic rupture of a high-pressure pipeline can be highly relevant, especially when the crater uncovers other pipelines, which could undergo a domino effect with a significant increase of the consequences on people or on the environment. However, this scenario has been only partially studied in the literature. To assess the influence of the pipeline parameters on the dimensions of the resulting crater, a statistical analysis of accidental ruptures of buried natural gas pipelines that have involved the formation of a crater was carried out. Mathematical expressions are proposed to describe the proportionality relationships found, which can be very useful to support adequate separation distances in the design and construction of parallel corridors of pipelines after appropriate escalating effects are considered. Finally, detailed event trees were developed to calculate the probability of occurrence of the final outcomes, as well as the identified domino sequences, based on a qualitative and quantitative analysis of the data. The study of these accident scenarios, based on actual cases, represents a useful and needed advance in risk analysis of natural gas transportation through pipelines.     

Ozone facilitated degradation of caffeine using Ce-TiO2 catalyst

The ozone initiated oxidation of 1,3,7-trimethylxanthine (caffeine), commonly found in wastewaters as model compound is reported using cerium (Ce)/titanium dioxide (TiO₂) as catalyst. The effect of pH and loading of ceria on titania were investigated. Effect of reaction conditions on degradation of caffeine based on their pseudo first-order rate constants were compared. The combination of catalyst Ce-TiO₂ and ozone aeration significantly enhanced the degradation of caffeine compared to uncatalysed ozonation. The oxidation of caffeine ensued via the free radical mechanism, through enhanced ozone decomposition into OH radicals. Ce/TiO₂(0.5?wt%) showed good activity in degradation of caffeine at pH 6, in both natural stream and river water samples showing about 60% total organic carbon removal in 2?h ozonation period. Using liquid chromatography-mass spectroscopy, degradation products were analysed. A reaction intermediate and one final product were positively identified. Nano-catalysts with different loadings of Ce on TiO₂ synthesized by sol-gel route were characterized by scanning electron microscope, transmission electron microscopy, BET and powder X-ray diffraction spectrum techniques. The results showed that the material retained a highly ordered mesoporous structure and possessed large surface area.     

砷尾矿污染土壤的细菌群落结构多样性及其相关环境影响因子分析

以湖南石门雄黄尾矿污染土壤为对象,研究纵向不同深度、横向不同距离土样中的重金属污染程度以及细菌群落结构变化规律,查明砷污染土壤的核心微生物组成并将其与土壤理化指标进行共存网络图分析。结果表明:该尾矿区的土壤各项重金属指标严重超标,尤以铅(626.54 mg·kg^?1,Ei=105.48)、砷(1804.75 mg·kg^?1,Ei=565.75)、镉(31.46 mg·kg^?1,Ei=7491.5)的生态危害性最强;土壤采样深度与重金属综合潜在生态风险指数(RI)呈显著正相关(r=0.79,P=0.000),而横向样品中RI与采样距离显著负相关(r=?0.85,P=0.000)。在污染土壤中,变形杆菌门(Proteobacteria,54.35%±17.16%)和放线杆菌门(Actinobacteria,22.39%±10.64%)占主导地位,属层级中假单孢杆菌属(Pseudomonas,16.47%±11.84%)、不动杆菌属(Acinetobacter,8.07%±7.11%)以及硫酸状杆菌属(Acidithiobacillus,7.53%±14.68%)相对丰度较高;而26个共享类群占据了该尾矿污染土壤中微生物群落总平均相对丰度90%以上,尽管不同属的具体相对丰度在不同样品间的分布趋势差异较大。纵剖采集的污染土样中,铁原体属(Ferroplasma)、硫酸状杆菌属(Acidithiobacillus)、硫化杆菌属(Sulfobacillus)、乳杆菌属(Lactobacillus)和硝化螺旋菌属(Nitrospira)占优势,与理化的共存网络图分析(相关系数|r|≥0.6,P<0.05)显示部分类群与亚铁、游离态砷和镉成显著正相关,而与pH成显著负相关;横向采集的土样中,以嗜酸菌属(Acidiphilium)、假单孢杆菌属(Pseudomonas)、棒状杆菌属(Corynebacterium)、硫杆菌属(Thiobacillus)等为主,部分类群与总砷、铅成显著正相关,而与结合态或包蔽型砷成显著负相关。综上,该研究不仅对目标区域尾矿不同重金属污染程度进行了分析,同时探讨了污染土壤中核心响应类群的组成多样性,为筛选潜在重金属抗性菌群或工程菌群提供理论基础。     

Effects of exogenous acylated homoserine lactones on biofilms in biofilters for gaseous toluene treatment

● Biofilm formation was enhanced by exogenous AHLs. ● EPS production and microbial adhesive strength of biofilm were promoted. ● Exogenous AHLs improved the performance of biofilters treating toluene. Biofilters are typical biofilm reactors, and they usually have poor biofilm formation resulting in limited reactor performance. Exogenous acylated homoserine lactones (AHLs) can enhance biofilm formation in many bioreactors based on quorum sensing regulation. However, their effect on biofilm in biofilters utilized for volatile organic compound (VOC) removal is unknown and needs to be investigated. In this study, the effects of the exogenous AHLs on biofilters for gaseous toluene removal were investigated. Analysis of biofilms in biofilters showed that the addition of exogenous AHLs considerably enhanced biofilm growth; the average biofilm concentration increased by 18%. Furthermore, the average biofilm coverage proportions in biofilters with and without exogenous AHLs were 17 % and 13 %, respectively, demonstrating the positive effect of exogenous AHLs on biofilm coverage. In particular, exogenous AHLs promoted the production of extracellular polymeric substances and the microbial adhesive strength of the biofilm. In addition, the exogenous AHLs showed no significant effect on the gaseous toluene removal efficiency of the biofilter. These results show that exogenous AHLs can enhance biofilm formation and can guide the application of exogenous AHLs in VOC biofilters.     

臭氧氧化—湿式钙法吸收工艺对烟气的同时脱硫脱硝

采用臭氧氧化—湿式钙法吸收工艺对模拟烟气进行同时脱硫脱硝处理。O₃于150 ℃下具有较高的热稳定性,可将NO氧化为高价态氮氧化物,且NO氧化率随n（O₃）∶n（NO）的增大而逐渐提高。烟气中SO₂和H₂O的存在对NO氧化率的影响不大。O₃对SO₂的氧化率较低,约为5%。3%（w）石灰石浆液对SO₂的吸收率接近100%,NO_x吸收率随n（O₃）∶n（NO）的增大而逐渐提高,当n（O₃）∶n（NO）为1.6时NO_x吸收率可达约65%。SO₂能促进吸收液对NO_x的脱除。石灰石浆液中加入0.2%（w）的（NH₄）₂SO₃或Na₂SO₃后NO_x吸收率可达约85%或82%,且吸收率随添加剂加入量的增加而提高,添加（NH₄）₂SO₃的NO_x吸收率略高于添加Na₂SO₃。     

聚硅酸钛制备及其助凝特性

采用在活化硅酸制备过程中加入适量Ti Cl4的方法,试制了一种新型无机高分子助凝剂—聚硅酸钛。研究了不同[Si]/[Ti]条件下制备的聚硅酸钛在固定p H值的水中分散物的粒径和Zeta电位随着活化时间的变化趋势,并与活化硅酸作比较。结果表明,在Si/Ti=20,活化48 h的条件下能制备出较为稳定的聚硅酸钛。与活化硅酸相比,聚硅酸钛在水中的分散物具有较大的粒径和更高的Zeta电位。通过对比制备的活化硅酸和聚硅酸钛的红外图谱发现,聚硅酸钛中有TiO-Si键,证明钛离子参与了聚合反应,新生成的化学键提高了它的聚合度和稳定性。采用硫酸铝为混凝剂,聚硅酸钛为助凝剂进行混凝除浊实验。测定了絮凝体的Zeta电位和混凝沉淀后的上清液浊度,研究了硫酸铝投加量和混凝p H对聚硅酸钛助凝效果的影响。结果表明,投加适量的聚硅酸钛助凝剂,明显提高了混凝除浊效果且拓宽了有效混凝p H值的范围。     

pH对铝盐絮凝剂形态分布与混凝除氟性能的影响

对比研究了AlC13和3种不同碱化度的聚合氯化铝(PACl)在不同pH与投量下除氟效果,并对不同形态铝盐除氟机理进行了初步探讨.结果表明,pH对絮凝剂水解后铝形态分布及其除氟效果有重要影响.pH 5 ～6时,Al3+和Al2、Al3等低聚态铝为AlCl3主要形态,且AlCl3更易水解生成可将溶解态氟转化为颗粒态氟的Al(OH)3,从而较PACl具有更佳除氟效果.pH ＞7时,PACl较AlCl3具有更佳除氟效果,且增大PACl碱化度可促进氟的去除,这主要是由于具有较高Al13含量的PACl更容易与电负性F-结合所致;且絮凝剂混凝除氟絮体ζ电位越高,越利于F-在絮体表面吸附.